CN103380535B - Low-light (level) DSSC - Google Patents
Low-light (level) DSSC Download PDFInfo
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- CN103380535B CN103380535B CN201280009011.5A CN201280009011A CN103380535B CN 103380535 B CN103380535 B CN 103380535B CN 201280009011 A CN201280009011 A CN 201280009011A CN 103380535 B CN103380535 B CN 103380535B
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- electrode
- oxide semiconductor
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- 150000002894 organic compounds Chemical class 0.000 claims abstract description 126
- 239000004065 semiconductor Substances 0.000 claims abstract description 79
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 6
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 68
- 229910052799 carbon Inorganic materials 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical group [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 7
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 7
- 150000004032 porphyrins Chemical group 0.000 claims description 7
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 125000002345 steroid group Chemical group 0.000 claims 3
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000000975 dye Substances 0.000 description 57
- 238000007789 sealing Methods 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 13
- 150000003431 steroids Chemical group 0.000 description 11
- 150000002926 oxygen Chemical class 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
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- 229930195733 hydrocarbon Natural products 0.000 description 8
- 238000005286 illumination Methods 0.000 description 8
- -1 pyridiniujm Chemical compound 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
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- MVDKKZZVTWHVMC-UHFFFAOYSA-N 2-hexadecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O MVDKKZZVTWHVMC-UHFFFAOYSA-N 0.000 description 4
- NDBRWMDPOBWCAI-UHFFFAOYSA-N CC(CCP(O)=O)(C)C Chemical class CC(CCP(O)=O)(C)C NDBRWMDPOBWCAI-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 229910001887 tin oxide Inorganic materials 0.000 description 4
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 3
- RUDATBOHQWOJDD-UHFFFAOYSA-N (3beta,5beta,7alpha)-3,7-Dihydroxycholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 RUDATBOHQWOJDD-UHFFFAOYSA-N 0.000 description 3
- 239000004380 Cholic acid Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 3
- 229960001091 chenodeoxycholic acid Drugs 0.000 description 3
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 3
- 229960002471 cholic acid Drugs 0.000 description 3
- 235000019416 cholic acid Nutrition 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DGABKXLVXPYZII-SIBKNCMHSA-N hyodeoxycholic acid Chemical compound C([C@H]1[C@@H](O)C2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 DGABKXLVXPYZII-SIBKNCMHSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
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- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
- H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Steroid Compounds (AREA)
Abstract
The present invention is a kind of low-light (level) DSSC, it comprises the 1st electrode having transparency carrier and arrange nesa coating on the transparent substrate, with the 1st electrode the 2nd electrode in opposite directions, be arranged on the oxide semiconductor layer on the 1st electrode or the 2nd electrode, be arranged on the 1st electrode and the 2nd interelectrode electrolyte, the coadsorbent being adsorbed on the photosensitive dye on oxide semiconductor layer and being adsorbed on together with photosensitive dye on oxide semiconductor layer, wherein, photosensitive dye is the metal complex that following formula (1) represents, coadsorbent contains the organic compound that following formula (2) etc. represents.In formula (1), M represents Ru, R
1, R
2, R
3and R
4separately represent monovalent cation, R
5and R
6separately represent halogen etc.In formula (2), n represents the integer of 0 ~ 5, R
7represent the univalent perssad etc. with pi-conjugated structure.
Description
Technical field
The present invention relates to low-light (level) DSSC.
Background technology
As photo-electric conversion element, DSSC, owing to can obtain cheapness, high-photoelectric transformation efficiency and receiving publicity, about DSSC, is carrying out various exploitation.
DSSC generally include work electrode, to electrode, connect work electrode and to the sealing of electrode, be filled in by the electrolyte in work electrode, the element cell space that surrounds electrode and sealing.And, the oxide semiconductor layer as electric layer that work electrode comprises transparency carrier, arranges nesa coating on the transparent substrate and be arranged on nesa coating.
In recent years, DSSC is not only used as outdoor solar cell, is also being used as the power supply etc. of indoor various electronic equipments.
But, know, usually, under the environment of the low-light (level)s such as indoor (below 10000 luxs), the generation electric current of DSSC and generation voltage drop.This is because the light quantity of incidence reduces, causing short circuit current to decline, producing leakage current as between the nesa coating on the oxide semiconductor layer of electric layer and transparency carrier and electrolyte, open circuit voltage being declined.Because photoelectric conversion efficiency is directly proportional to short circuit current and open circuit voltage, therefore, if short circuit current, open circuit voltage decline, photoelectric conversion efficiency also reduces.So, even if need a kind of DSSC that also can improve short circuit current, open circuit voltage under the low-light (level) environment such as indoor.
Such as, in following patent documentation 1, someone proposes the I by reducing in electrolyte
3 -concentration reduce the absorption of electrolyte to incident light, improve light transmission, thus increase short circuit current.
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-251736 publication
Summary of the invention
But the DSSC recorded in above-mentioned patent documentation 1 is hard to say has sufficient light transfer characteristic under low-light (level) environment.
The present invention completes in view of the foregoing, has the low-light (level) DSSC of excellent light transfer characteristic under aiming to provide a kind of low-light (level) environment below 10000 luxs.
In order to solve the problem, present inventor conducts in-depth research, and consequently, expects under low-light (level) environment, only reduces the I in electrolyte
3 -whether concentration fully can not improve light transfer characteristic.And present inventor expects, will improve light transfer characteristic under low-light (level) environment, it is effective for increasing open circuit voltage, in order to increase open circuit voltage, must reduce leakage current.So present inventor is conceived to the photosensitive dye be adsorbed on oxide semiconductor layer and is studied.Its result, present inventor expects, if the region of not adsorbing anything between the photosensitive dye being adsorbed on oxide semiconductor layer surface increases, then whether in this region, electronics easily shifts to electrolyte etc. from oxide semiconductor layer, its result, and leakage current increases.For this reason, present inventor expects coadsorbent to be adsorbed on oxide semiconductor layer together with the photosensitive dye being called N719, N3.But, when measuring photoelectric conversion efficiency under the irradiance of 1sun representing sunlight strength, sometimes obtain low-down value.Envision thus, lower photoelectric conversion efficiency can be obtained under low-light (level) environment.But, the coadsorbent with ad hoc structure is being adsorbed onto after on oxide semiconductor layer together with the photosensitive dyes such as N719, N3, be surprised to find that, compared with the photoelectric conversion efficiency recorded out of doors, under low-light (level) environment, DSSC demonstrates very high photoelectric conversion efficiency.Therefore, present inventor has carried out more deep research, found that, can above-mentioned problem be solved by the photosensitive dye with ad hoc structure and the combination that is adsorbed on the specific coadsorbent on oxide semiconductor layer together with this photosensitive dye, and this completes the present invention.
Namely, the present invention is a kind of low-light (level) DSSC, it comprises the 1st electrode having transparency carrier and be arranged on the nesa coating on above-mentioned transparency carrier, with above-mentioned 1st electrode the 2nd electrode in opposite directions, be arranged on the oxide semiconductor layer on above-mentioned 1st electrode or above-mentioned 2nd electrode, be arranged on above-mentioned 1st electrode and above-mentioned 2nd interelectrode electrolyte, the coadsorbent being adsorbed on the photosensitive dye on above-mentioned oxide semiconductor layer and being adsorbed on together with above-mentioned photosensitive dye on above-mentioned oxide semiconductor layer, above-mentioned photosensitive dye is the metal complex that following formula (1) represents, above-mentioned coadsorbent contains the organic compound being selected from following formula (2) and representing, at least one organic compound in the organic compound that following formula (3) represents and the organic compound that following formula (4) represents.
[changing 1]
(in formula (1), M represents Ru, R
1, R
2, R
3and R
4separately represent monovalent cation, R
5and R
6separately represent halogen ,-H ,-CN ,-NCS or-NCO.）
[changing 2]
(in formula (2), n represents the integer of 0 ~ 5, R
7represent and there is the univalent perssad of pi-conjugated structure or there is the univalent perssad of steroid backbone.）
[changing 3]
(in formula (3), W represents carbon atom or silicon atom, Y
1, Y
2, Y
3and Y
4separately represent that hydrogen atom, carboxyl, carbon number are the replacement of 1 ~ 6 or are the replacement of 3 ~ 20 or the alkyl without replacement without the alkoxyl replaced or carbon number, Y
1, Y
2, Y
3and Y
4in one represent carbon number be 3 ~ 20 replacement or without the alkyl replaced, in all the other at least two represent carboxyls or carbon number be 1 ~ 6 replacement or without the alkoxyl replaced.）
[changing 4]
(in formula (4), Y
5, Y
6and Y
7separately represent that hydroxyl or carbon number are the replacement of 3 ~ 20 or the alkyl without replacement, Y
5, Y
6and Y
7in one or two represent carbon numbers be 3 ~ 20 replacement or without replace alkyl, all the other represent hydroxyl.）
According to DSSC of the present invention, as photosensitive dye, use the photosensitive dye that above formula (1) represents.This photosensitive dye has high-selenium corn efficiency under short wavelength.On the other hand, in the room lights such as fluorescent lamp, comprise the light of a large amount of short wavelength, and not too comprise the light of long wavelength.Therefore, the photosensitive dye that formula (1) represents is especially applicable as the photosensitive dye of indoor DSSC, compared with the Z907 of black dyestuff, side chain length, can realize excellent light transfer characteristic.And coadsorbent contains at least one organic compound in organic compound that the organic compound, the following formula (3) that are selected from above formula (2) and represent represent and the organic compound that following formula (4) represents.Here, the organic compound that formula (2) represents contains the univalent perssad with pi-conjugated structure or the univalent perssad with steroid backbone.Here, the univalent perssad with pi-conjugated structure and the univalent perssad with steroid backbone all have plane shape and not easily Free Transform.In addition, in the organic compound that formula (3) represents, Y
1, Y
2, Y
3and Y
4in at least one represent carbon number be 3 ~ 20 replacement or without replace alkyl, at least two in all the other is carboxyl or alkoxyl.In this case, because at least two carboxyls or alkoxyl are adsorbed on oxide semiconductor layer, therefore, the organic compound not easily Free Transform that formula (3) represents.In addition, the organic compound that formula (4) represents has PO base.Here, P is than C(carbon atom contained in carboxyl and alkoxyl) there is low electronegativity.Therefore, PO base not easily becomes ion, not easily departs from from oxide semiconductor layer.So PO base is adsorbed on oxide semiconductor layer firmly.Therefore, even if organic compound is not the organic compound represented such as formula (3), there is the also not easily Free Transform such as at least two carboxyls like that.Like this, above-mentioned coadsorbent contains the organic compound of not easily Free Transform when being adsorbed on oxide semiconductor layer surface.Therefore, do not need to be unnecessarily coadsorbent installation space on the surface of oxide semiconductor layer.So, photosensitive dye can be adsorbed on the surface of oxide semiconductor layer fully.In addition, on the surface of oxide semiconductor layer, coadsorbent can be adsorbed on and not be adsorbed with on the region of photosensitive dye.Oxide semiconductor layer surface be not adsorbed with in the region of photosensitive dye, the place of electro transfer (inversion electron transfer) can be produced between oxide semiconductor layer and electrolyte, in the present invention, be adsorbed on this region by coadsorbent, can fully suppress inversion electron to shift.Its result, can reduce leakage current, thus can increase open circuit voltage under low-light (level) environment.Thus, low-light (level) DSSC of the present invention has excellent light transfer characteristic.
In above-mentioned DSSC, in the organic compound preferably represented in above formula (2) ~ (4), the oxygen atom (O) of the OH base in the organic compound that above formula (2) ~ (4) represent and be 0.7 ~ 3nm apart from the length between this oxygen atom (O) atom farthest.
In this case, the length of above-mentioned photosensitive dye is about 1.5nm, therefore, compared with the situation being less than 0.7nm with the length of above-mentioned organic compound, can reduce leakage current more fully.In addition, with the length of above-mentioned organic compound more than 3nm situation compared with, easily occurred by the electron injection of electrolyte to photosensitive dye, light transfer characteristic can be improved further.
In above-mentioned DSSC, above-mentioned coadsorbent contains the two kinds of organic compounds be selected from organic compound that above formula (2) ~ (4) represent, or also can containing being selected from organic compound that above formula (2) ~ (4) represent and the organic compound that following formula (X) represents.
[changing 5]
(in formula (X), A
1~ A
3separately represent hydrogen atom or methyl, A
4represent hydroxyl or carboxyl.）
Here, preferred above-mentioned coadsorbent contains the 1st organic compound and the 2nd organic compound, following 1st length of described 1st organic compound is larger than following 2nd length of described 2nd organic compound, wherein, described 1st organic compound is in the organic compound being selected from the organic compound that above formula (2) ~ (4) represent, in the organic compound that above formula (2) ~ (4) represent from the oxygen atom of OH base to being the organic compound of 0.7 ~ 3nm apart from the 1st length this oxygen atom atom farthest, 2nd organic compound is in the organic compound being selected from the organic compound that above formula (2) ~ (4) and formula (X) represent, in the organic compound that above formula (2) ~ (4) or formula (X) represent from the oxygen atom of OH base to being the organic compound of 0.1 ~ 0.7nm apart from the 2nd length this oxygen atom atom farthest.
In this case, the 2nd organic compound enters between the 1st organic compound, can suppress more fully to associate between the 1st organic compound.
The R of above formula (2)
7in, preferably, the above-mentioned univalent perssad with pi-conjugated structure is the univalent perssad with merocyanine skeleton, phenyl skeleton, guanidine skeleton, pyridine skeleton or porphyrin skeleton, and the above-mentioned univalent perssad with steroid backbone is the univalent perssad that following formula (5) represents.
[changing 6]
There is the univalent perssad of steroid backbone
(in formula (5), R
34, R
35and R
36separately represent hydrogen atom or hydroxyl.）
In this case, due to leakage current can be reduced further, thus under low-light (level) environment, open circuit voltage can be increased further.
The R of above formula (2)
7in, the above-mentioned univalent perssad with pi-conjugated structure preferably has the univalent perssad of merocyanine skeleton or guanidine skeleton.In this case, due to leakage current can be reduced further, thus open circuit voltage can be increased further under low-light (level) environment.
In above formula (1), preferred R
1, R
2, R
3and R
4in at least one be hydrogen ion.In this case, because oxide semiconductor layer is on the surface containing ester bond, the electron injection efficiency of oxide semiconductor layer is improved further.
In above formula (1), preferred R
1, R
2, R
3and R
4in at least one be hydrogen ion, all the other are the ammonium salt of monovalence.In this case, absorptivity improves further.
In above formula (1), preferred R
5and R
6for-NCS.In this case, absorptivity improves further, improves further from electrolytical electron injection efficiency.
In above-mentioned low-light (level) DSSC, preferred coadsorbent is 0.1 ~ 1 relative to the mol ratio of photosensitive dye.
If coadsorbent relative to the mol ratio of photosensitive dye, then with not compared with the situation of above-mentioned scope, more effectively can reduce leakage current, and generation current can be made to increase further in above-mentioned scope.
In above-mentioned low-light (level) DSSC, preferred above-mentioned electrolyte contains by I
-and I
3 -the oxidation-reduction pair formed, the I in above-mentioned electrolyte
3 -concentration is at below 0.006mol/L.
In this case, due to the I of transport electrons
3 -concentration low, thus can reduce leakage current further, increase open circuit voltage further.Thus, light transfer characteristic can be improved further.
In addition, in the present invention, " low-light (level) " refers to the illumination of below 10000 luxs.
According to the present invention, provide a kind of low-light (level) DSSC under low-light (level) environment with excellent light transfer characteristic.
Accompanying drawing explanation
Fig. 1 is the sectional view of the execution mode showing low-light (level) DSSC of the present invention.
Embodiment
Below, with reference to accompanying drawing, embodiments of the present invention are described in detail.
Fig. 1 is the sectional view of an execution mode of display DSSC of the present invention.
As shown in Figure 1, DSSC 100 uses under low-light (level) environment, it comprise work electrode 10, with work electrode 10 in opposite directions to electrode 20 and be connected work electrode 10 and the annular sealing portion 30 to electrode 20, in by work electrode 10, the element cell space S that formed electrode 20 and sealing 30, be filled with electrolyte 40.
Work electrode 10 comprises by transparency carrier 11 and is arranged on the transparent conductive substrate 15 that the nesa coating 12 on transparency carrier 11 is formed and at least one oxide semiconductor layer 13 be arranged on the nesa coating 12 of transparent conductive substrate 15.Oxide semiconductor layer 13 is configured in the inner side of sealing 30.In addition, oxide semiconductor layer 13 is adsorbed with photosensitive dye and coadsorbent simultaneously.In the present embodiment, form the 1st electrode by transparent conductive substrate 15, form the 2nd electrode by electrode 20.
Here, as photosensitive dye, use the metal complex that following formula (1) represents.The organic compound that coadsorbent contains organic compound that following formula (2) represents, following formula (3) represents or the organic compound that following formula (4) represents.The organic compound that formula (2) ~ (4) represent can individually use, and also can be used in combination.
[changing 7]
(in formula (1), M represents Ru, R
1, R
2, R
3and R
4separately represent monovalent cation, R
5and R
6separately represent halogen ,-H ,-CN ,-NCS or-NCO.）
[changing 8]
(in formula (2), n represents the integer of 0 ~ 5, R
7represent and there is the univalent perssad of pi-conjugated structure or there is the univalent perssad of steroid backbone.）
[changing 9]
(in formula (3), W represents carbon atom or silicon atom, Y
1, Y
2, Y
3and Y
4separately represent that hydrogen atom, carboxyl, carbon number are the replacement of 1 ~ 6 or are the replacement of 3 ~ 20 or the alkyl without replacement without the alkoxyl replaced or carbon number, Y
1, Y
2, Y
3and Y
4in one represent carbon number be 3 ~ 20 replacement or without the alkyl replaced, in all the other at least two represent carboxyls or carbon number be 1 ~ 6 replacement or without the alkoxyl replaced.）
[changing 10]
(in formula (4), Y
5, Y
6and Y
7separately represent that hydroxyl or carbon number are the replacement of 3 ~ 20 or the alkyl without replacement, Y
5, Y
6and Y
7in one or two represent carbon numbers be 3 ~ 20 replacement or without replace alkyl, remaining represents hydroxyl.）
To electrode 20, there is conductive board 21 and be arranged on the catalyst layer 22 of promotion catalytic reaction of work electrode 10 side of conductive board 21.
According to above-mentioned DSSC 100, as photosensitive dye, use the photosensitive dye that above formula (1) represents.This photosensitive dye has high-selenium corn efficiency under short wavelength.On the other hand, comprise the light of a large amount of short wavelength in the light that fluorescent lamp etc. are indoor, and not too comprise the light of long wavelength.Therefore, the photosensitive dye that formula (1) represents is especially applicable as the photosensitive dye of indoor DSSC, compared with the Z907 of black dyestuff, side chain length, can realize excellent light transfer characteristic.And coadsorbent contains at least one in organic compound that the organic compound, the following formula (3) that are selected from above formula (2) and represent represent and the organic compound that following formula (4) represents.Here, the organic compound that formula (2) represents contains the univalent perssad with pi-conjugated structure or the univalent perssad with steroid backbone.Here, the univalent perssad with pi-conjugated structure and the univalent perssad with steroid backbone all have plane shape and are not easily freely out of shape.In addition, in the organic compound that formula (3) represents, Y
1, Y
2, Y
3and Y
4in one represent carbon number be 3 ~ 20 replacement or without replace alkyl, at least two in all the other is carboxyl or alkoxyl.In this case, because at least two carboxyls or alkoxyl are adsorbed on oxide semiconductor layer 13, therefore, the organic compound that formula (3) represents not easily freely is out of shape.In addition, the organic compound that formula (4) represents has PO base.Here, P is than C(carbon atom contained in carboxyl and alkoxyl) there is low electronegativity.Therefore, PO base not easily becomes ion, not easily departs from from oxide semiconductor layer 13.So PO base is adsorbed on oxide semiconductor layer 13 firmly.Therefore, even if organic compound is not the organic compound represented such as formula (3) like that at least have two carboxyls etc., be also not easily freely out of shape.Like this, above-mentioned coadsorbent contains the organic compound of the not easily Free Transform when the adsorption of oxide semiconductor layer 13.Therefore, do not need unnecessarily on the surface of oxide semiconductor layer 13 for coadsorbent provides space.So, photosensitive dye can be made to be adsorbed on fully on the surface of oxide semiconductor layer 13.In addition, on the surface of oxide semiconductor layer 13, coadsorbent can be adsorbed on and not be adsorbed with on the region of photosensitive dye.In the region not being adsorbed with photosensitive dye on oxide semiconductor layer 13 surface, the place of electro transfer (inversion electron transfer) can be produced between oxide semiconductor layer 13 and electrolyte 40, in DSSC 100, because coadsorbent adsorbs in this region, thus can fully suppress inversion electron to shift, its result, can reduce leakage current, thus can increase open circuit voltage under low-light (level) environment.So low-light (level) DSSC 100 has excellent light transfer characteristic.
In addition, as described above, the photosensitive dye used in low-light (level) DSSC 100 has high-selenium corn efficiency under short wavelength, compared with the Z907 of black dyestuff, side chain length, can realize excellent light transfer characteristic.On the other hand, comprise the light of a large amount of short wavelength in the light that fluorescent lamp etc. are indoor, and not too comprise the light of long wavelength.Therefore, low-light (level) DSSC 100 is especially applicable as indoor DSSC.
Then, to work electrode 10, be described in detail to electrode 20, sealing 30, electrolyte 40, photosensitive dye and coadsorbent.
(work electrode)
As described above, work electrode 10 has transparency carrier 11, is arranged on the nesa coating 12 on transparency carrier 11 and is arranged at least one oxide semiconductor layer 13 on nesa coating 12.
As long as form the material that the material of transparency carrier 11 is such as transparent, as this kind of transparent material, can be such as the glass such as pyrex, soda-lime glass, ultra-clear glasses, quartz glass, PETG (PET), PEN (PEN), Merlon (PC), polyether sulfone (PES) etc.The thickness of transparency carrier 11 suitably can be determined according to the size of low-light (level) DSSC 100, without particular restriction, such as, the scope of 50 μm ~ 10000 μm.
As the material forming nesa coating 12, such as, can be tin-doped indium oxide (Indium-Tin-Oxide:ITO), tin oxide (SnO
2), the conductive metal oxide such as fluorine doped tin oxide (Fluorine-doped-Tin-Oxide:FTO).Nesa coating 12 can be made up of individual layer, and the multilayer laminate that also can be made up of different conductive metal oxide is formed.When nesa coating 12 is made up of individual layer, consider from the angle with high-fire resistance and chemical proofing, preferably clear conducting film 12 is made up of FTO.If use as nesa coating 12 laminate be made up of multilayer, then because of can reflect each layer characteristic and preferably.Wherein, the laminate of the layer be made up of ITO and the layer be made up of FTO is preferably used.In this case, the nesa coating 12 with high conductivity, thermal endurance and chemical proofing can be realized.The thickness of nesa coating 12 is such as the scope of 0.01 μm ~ 2 μm.
Oxide semiconductor layer 13 is made up of oxide semiconductor particle.Oxide semiconductor particle is such as by titanium oxide (TiO
2), zinc oxide (ZnO), tungsten oxide (WO
3), niobium oxide (Nb
2o
5), strontium titanates (SrTiO
3), tin oxide (SnO
2), indium oxide (In
3o
3), zirconia (ZrO
2), thallium oxide (Ta
2o
5), lanthana (La
2o
3), yittrium oxide (Y
2o
3), holimium oxide (Ho
2o
3), bismuth oxide (Bi
2o
3), cerium oxide (CeO
2), aluminium oxide (Al
2o
3) or their two or more formations.
As long as the thickness of oxide semiconductor layer 13 is such as at 0.5 ~ 50 μm.
(to electrode)
As described above, electrode 20 is comprised be arranged on work electrode 10 side in conductive board 21 and conductive board 21 promotion to the conductive catalyst oxidant layer 22 of the reduction reaction on electrode 20 surface.
Conductive board 21 is such as made up of the corrosion resistant metallic materials such as titanium, nickel, platinum, molybdenum, tungsten, the material that is formed with the film be made up of electroconductive oxides such as ITO, FTO on above-mentioned transparency carrier 11.The thickness of conductive board 21 suitably can be determined according to the size of low-light (level) DSSC 100, without particular restriction, such as, at 0.005 ~ 0.1mm.
Catalyst layer 22 is made up of platinum, carbon-based material or electroconductive polymer etc.Here, as carbon system macromolecular material, carbon nano-tube can use well.
(sealing)
As sealing 30, such as, can be the resins such as thermoplastic resin, ultraviolet curable resin and vinyl alcohol polymer such as ionomer, ethylene-vinyl acetate anhydride copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer.
(electrolyte)
Electrolyte 40 is containing such as I
-/ I
3 -deng oxidation-reduction pair and organic solvent.As organic solvent, acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propene carbonate, diethyl carbonate, gamma-butyrolacton etc. can be used.As oxidation-reduction pair, such as, except I
-/ I
3 -in addition, can also be that the electricity such as bromine/bromide ion are right.In addition, also gelating agent can be added in above-mentioned volatile solvent.In addition, the ionic liquid electrolyte that electrolyte 40 also can be formed by the mixture of ionic liquid and volatile ingredient is formed.As ionic liquid, can use and such as be the known salt compounded of iodine such as pyridiniujm, imidazole salts, triazolium salt and the normal temperature fuse salt being in molten condition near room temperature.As this kind of normal temperature fuse salt, such as, can use two (trifluoromethyl sulfonyl) imines of 1-ethyl-3-methylimidazole aptly.In addition, as volatile ingredient, can be above-mentioned organic solvent, LiI, I
2, 4-tert .-butylpyridine, N-tolimidazole etc.
In addition, electrolyte 40 contains by I
-/ I
3 -the oxidation-reduction pair formed, I
3 -concentration preferably at below 0.006mol/L, be more preferably 0 ~ 6 × 10
-6mol/L, most preferably is 0 ~ 6 × 10
-8mol/L.In this case, owing to carrying the I of electronics
3 -concentration low, thus can reduce leakage current further.Therefore, open circuit voltage can be increased further, thus light transfer characteristic can be improved further.
(photosensitive dye)
As photosensitive dye, as described above, the metal complex that following formula (1) represents can be used.
[changing 11]
In formula (1), M represents Ru, R
1, R
2, R
3and R
4separately represent monovalent cation, R
5and R
6separately represent halogen ,-H ,-CN ,-NCS or-NCO.
As monovalent cation, can be hydrogen ion, monovalence ammonium salt and sodium ion etc.
Wherein, preferred R
1, R
2, R
3and R
4be hydrogen ion.In this case, easily can synthesize photosensitive dye, and synthesize with low cost.
In addition, also can be R
1, R
2, R
3and R
4in at least 1 be hydrogen ion, remaining is ammonium salt.In this case, absorptivity improves further.
Ammonium salt following formula (6) represents.
[changing 12]
In formula (6), R
8, R
9, R
10and R
11separately represent that hydrogen atom or carbon number are the replacement of 1 ~ 6 or the alkyl without replacement.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can be the aryl such as cycloalkyl, phenyl or naphthyl etc. such as the alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, vinyl, cyclopenta, cyclohexyl.Substituted hydrocarbon radical is that the hydrogen atom of alkyl is replaced to the group after other substituting groups, as this kind of substituting group, such as, can be the halogens etc. such as-Cl ,-F ,-I.
Here, preferred R
8, R
9, R
10and R
11alkyl all for being made up of butyl.In this case, with R
8, R
9, R
10and R
11be not that the situation of butyl is compared entirely, absorptivity improves further.
In addition, in formula (1), as R
5and R
6halogen, can be such as-Cl ,-Br ,-I and-F etc., wherein, be preferably-I.
R
5and R
6during for-NCS, absorptivity improves further, and the electron injection efficiency from electrolyte 40 improves further, thus preferably.
(coadsorbent)
As coadsorbent, as has been described, can the organic compound that represents as shown in the formula (2) of example.Here, organic compound is only made up of non-metallic atom.
[changing 13]
In formula (2), n represents the integer of 0 ~ 5, R
7represent and there is the univalent perssad of pi-conjugated structure or there is the univalent perssad of steroid backbone.
At the R of above formula (2)
7in, as the univalent perssad with pi-conjugated structure, can be the univalent perssad with merocyanine skeleton, phenyl skeleton, guanidine skeleton, pyridine skeleton and porphyrin skeleton.
Here, the univalent perssad with merocyanine skeleton represents with following formula (7).
[changing 14]
There is the univalent perssad of merocyanine skeleton
In formula (7), R
12represent that hydrogen atom ,-CN or carbon number are the alkyl of 1 ~ 5, R
13, R
14, R
16and R
17represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5, R
15to be carbon number be 1 ~ 5 the phenyl that replaces of alkoxyl or represent with following formula (8).R
16and R
17also can be combined with each other, form 5 rings or 6 rings.
[changing 15]
In formula (8), X
1, X
2, X
3and X
4separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can be the aryl such as cycloalkyl, phenyl or naphthyl etc. such as the alkyl such as methyl, ethyl, propyl group, butyl, amyl group, vinyl, cyclopenta.Substituted hydrocarbon radical is that the hydrogen atom of alkyl is replaced to the group after other substituting groups, as this kind of substituting group, such as, can be the halogens etc. such as-Cl ,-F ,-I.
The univalent perssad (phenyl) with phenyl skeleton represents with following formula (9).
[changing 16]
There is the univalent perssad of phenyl skeleton
In formula (9), R
18represent that hydrogen atom, hydroxyl or carbon number are the replacement of 1 ~ 6 or the alkyl without replacement, Y
8represent singly-bound or-CY
9(Y
10) CO-.Y
9and Y
10separately represent that hydrogen atom or carbon number are the replacement of 1 ~ 6 or the alkyl without replacement.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can use the alkyl identical with the alkyl in formula (6).In addition, the alternatively substituting group of hydrocarbon, such as, can use the substituting group identical with the substituting group of the alkyl in formula (6).
The univalent perssad (guanidine radicals) with guanidine skeleton represents with following formula (10).
[changing 17]
There is the univalent perssad of guanidine skeleton
In formula (10), R
19, R
20, R
21and R
22separately represent that hydrogen atom or carbon number are the replacement of 1 ~ 6 or the alkyl without replacement.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can use the alkyl identical with the alkyl in formula (6).In addition, the alternatively substituting group of hydrocarbon, such as, can use the substituting group identical with the substituting group of the alkyl in formula (6).
The univalent perssad (pyridine radicals) with pyridine skeleton represents with following formula (11).
[changing 18]
There is the univalent perssad of pyridine skeleton
In formula (11), R
23, R
24and R
25separately represent that hydrogen atom or carbon number are the replacement of 1 ~ 6 or the alkyl without replacement, R
23and R
24also can be combined with each other, form 5 ~ 6 rings.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can use the alkyl identical with the alkyl in formula (6).In addition, the alternatively substituting group of hydrocarbon, such as, can use the substituting group identical with the substituting group of the alkyl in formula (6).
The univalent perssad with porphyrin skeleton such as represents with following formula (12).
[changing 19]
There is the univalent perssad of porphyrin skeleton
In formula (12), R
27, R
28, R
29, R
30, R
31, R
32and R
33separately represent that hydrogen atom or carbon number are the replacement of 1 ~ 6 or the alkyl without replacement.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can use the group identical with the alkyl in formula (6).In addition, the alternatively substituting group of hydrocarbon, such as, can use the substituting group identical with the substituting group of the alkyl in formula (6).
In addition, as the univalent perssad with steroid backbone, such as, the univalent perssad that following formula (5) represents can be used.
[changing 20]
There is the univalent perssad of carrier framework
In formula (5), R
34, R
35and R
36separately represent hydrogen atom or hydroxyl.
In formula (2), n represents the integer of 0 ~ 5.N is preferably the integer of 0 ~ 3, is more preferably the integer of 0 ~ 2.
As the object lesson of coadsorbent with merocyanine skeleton, such as, it can be the organic compound etc. that following structural formula (A) and following structural formula (B) represent.
[changing 21]
[changing 22]
As the coadsorbent with phenyl skeleton, such as, can be 3-benzenpropanoic acid and 4-hydroxyphenyl pyravate etc.
As the object lesson of coadsorbent with guanidine skeleton, such as, it can be 4-guanidine radicals butyric acid etc.
As the object lesson of coadsorbent with pyridine skeleton, such as, can be 2,3-pyridinedicarboxylic acid, the 5-tert-butyl group-2-pyridine carboxylic acid and acidum nicotinicum etc.
As the object lesson of coadsorbent with porphyrin skeleton, such as, it can be the organic compound that following structural formula (C) represents.
[changing 23]
Or the coadsorbent with porphyrin skeleton also can be the organic compound that following structural formula (D) represents.
[changing 24]
As the object lesson of coadsorbent with steroid backbone, such as, can be deoxycholic aicd, chenodeoxycholic acid, cholic acid and hyodesoxycholic acid etc.
In addition, as coadsorbent, as has been described, the organic compound that following formula (3) also can be used to represent.
[changing 25]
In formula (3), W represents carbon atom or silicon atom, Y
1, Y
2, Y
3and Y
4separately represent that hydrogen atom, carboxyl, carbon number are the replacement of 1 ~ 6 or are the replacement of 3 ~ 20 or the alkyl without replacement without the alkoxyl replaced or carbon number, Y
1, Y
2, Y
3and Y
4in a replacement representing carbon number 3 ~ 20 or without the alkyl replaced, in all the other at least two represent carboxyls or carbon number be 1 ~ 6 replacement or without the alkoxyl replaced.
Here, when W is silicon atom, preferred Y
1, Y
2, Y
3and Y
4in at least one represent carbon number be 3 ~ 20 replacement or without the alkyl replaced, in all the other at least two represent carbon numbers be 1 ~ 6 replacement or without the alkoxyl replaced.In this case, coadsorbent more not easily departs from from oxide semiconductor layer 13.
When W is carbon atom, preferred Y
1, Y
2, Y
3and Y
4in at least one represent that carbon number is the replacement of 3 ~ 20 or without the alkyl replaced, in all the other at least two represent carboxyls.In this case, coadsorbent more not easily departs from from oxide semiconductor layer 13.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can use the alkyl identical with the alkyl in above formula (6).In addition, the alternatively substituting group of hydrocarbon, such as, can use the substituting group identical with the substituting group of the alkyl in formula (6).
As the object lesson of the organic compound that formula (3) represents, such as, can be 2-cetyl malonic acid (HDMA), decyl trimethoxy silane and trifluoro propyl trimethoxy silane.
In addition, as coadsorbent, as has been described, the organic compound that following formula (4) represents can also be used.
[changing 26]
In formula (4), Y
5, Y
6and Y
7separately represent that hydroxyl or carbon number are the replacement of 3 ~ 20 or the alkyl without replacement, Y
5, Y
6and Y
7in one or two represent carbon numbers be 3 ~ 20 replacement or without replace alkyl, remaining represents hydroxyl.
Here, can be Y
5, Y
6and Y
7in one represent hydroxyl, remaining represents above-mentioned alkyl, but be preferably Y
5, Y
6and Y
7in two represent hydroxyls, remaining represents above-mentioned alkyl.In this case, coadsorbent more not easily departs from from oxide semiconductor layer 13.
Above-mentioned alkyl can be straight chain also can be side chain, as above-mentioned alkyl, such as, can use the alkyl identical with the alkyl in above formula (6).In addition, the alternatively substituting group of hydrocarbon, such as, use the substituting group identical with the substituting group of the alkyl in formula (6).
As the object lesson of the organic compound that formula (4) represents, such as, can be two (3,3-dimethylbutyl) phosphinic acids (DINHOP) and positive decylphosphonic acid (DPA).
The oxygen atom (O) of the OH base in the organic compound that preferred formula (2) ~ (4) represent and be 0.7 ~ 3nm apart from the length between this oxygen atom (O) atom farthest.In this case, because the length of above-mentioned photosensitive dye is about 1.5nm, therefore, the length of the organic compound represented with formula (2) ~ (4) is less than compared with the situation of 0.7nm, can reduce leakage current fully further.In addition, the length of the organic compound represented with formula (2) ~ (4) more than 3.0nm situation compared with, electronics is easier to be injected into photosensitive dye from electrolyte 40, can improve the light transfer characteristic of low-light (level) DSSC 100 further.
Here, the oxygen atom (O) of the OH base in the organic compound that formula (2) ~ (4) in coadsorbent represent and can being calculated by molecular formula apart from the length between this oxygen atom (O) atom farthest.
In above-mentioned DSSC 100, coadsorbent can containing the two kinds of organic compounds be selected from organic compound that formula (2) ~ (4) represent.
Here, preferably, coadsorbent contains the 1st organic compound and the 2nd organic compound, and the 1st length of the 1st organic compound is larger than the 2nd length of the 2nd organic compound, wherein, 1st organic compound is in the organic compound that represents of formula (2) ~ (4), formula (2) ~ (4) represent in organic compound from the oxygen atom of OH base to being the organic compound of 0.7 ~ 3nm apart from the 1st length this oxygen atom atom farthest, 2nd organic compound is in the organic compound that represents of formula (2) ~ (4), in the organic compound that formula (2) ~ (4) represent from the oxygen atom of OH base to being the organic compound of 0.1 ~ 0.7nm apart from the 2nd length this oxygen atom atom farthest.
In this case, the 2nd organic compound easily enters between the 1st organic compound, can suppress more fully to associate between the 1st organic compound.
Or in above-mentioned DSSC 100, coadsorbent also can contain organic compound that formula (2) ~ (4) represent and the organic compound that following formula (X) represents.
[changing 27]
(in formula (X), A
1~ A
3separately represent hydrogen atom or methyl, A
4represent hydroxyl or carboxyl.）
Here, preferably, coadsorbent contains the 1st organic compound and the 2nd organic compound, and the 1st length of the 1st organic compound is larger than the 2nd length of the 2nd organic compound, wherein, 1st organic compound is in the organic compound that represents of formula (2) ~ (4), formula (2) ~ (4) represent in organic compound from the oxygen atom of OH base to being the organic compound of 0.7 ~ 3nm apart from the 1st length this oxygen atom atom farthest, 2nd organic compound is in the organic compound that represents of formula (X), in the organic compound that formula (X) represents from the oxygen atom of O H base to being the organic compound of 0.1 ~ 0.7nm apart from the 2nd length this oxygen atom atom farthest.
In this case, the 2nd organic compound easily enters between the 1st organic compound, can suppress more fully to associate between the 1st organic compound.
In addition, the 1st length of the 1st organic compound is preferably 0.7 ~ 2nm, and the 2nd length of the 2nd organic compound is preferably 0.1 ~ 0.5nm.
As the object lesson of above-mentioned 1st organic compound, can be such as deoxycholic aicd (1.5nm), chenodeoxycholic acid (1.5nm), cholic acid (1.5nm), 4-guanidine radicals butyric acid (1nm), 3-benzenpropanoic acid (0.9) nm, 2,3-pyridinedicarboxylic acid (0.9nm), 2-cetyl malonic acid (HDMA), two (3,3-dimethylbutyl) phosphinic acids (DINHOP) and the 5-tert-butyl group-2-pyridine carboxylic acid etc.The value of the numeric representation in bracket the 1st length.1st length of 2-cetyl malonic acid (HDMA) and two (3,3-dimethylbutyl) phosphinic acids (DINHOP) is respectively 0.9 ~ 1.4nm.
As the object lesson of above-mentioned 2nd organic compound, such as, can be the tert-butyl alcohol (0.4nm), PA (0.6nm) etc.The value of the numeric representation in bracket the 2nd length.
Here, the 2nd organic compound is preferably 0.5 ~ 10 relative to the mol ratio of the 1st organic compound, is more preferably 1 ~ 5.In this case, with not compared with the situation of above-mentioned scope, more effectively leakage current can be reduced.
Coadsorbent is generally 0.05 ~ 2 relative to the mol ratio of photosensitive dye, is preferably 0.1 ~ 1.Coadsorbent, relative to when the mol ratio of photoactivate fuel is in above-mentioned scope, with not compared with the situation of above-mentioned scope, effectively can reduces leakage current further, and generation current can be made to increase further.
Then, the manufacture method of above-mentioned low-light (level) DSSC 100 is described.
First, be ready to form nesa coating 12 on transparency carrier 11 and the transparent conductive substrate 15 obtained.
As the formation method of nesa coating 12, sputtering method, vapour deposition method, spray pyrolysis (SPD:Spray Pyrolysis Deposition) and CVD etc. can be used.
Then, nesa coating 12 forms oxide semiconductor layer 13.Oxide semiconductor layer 13 is formed by carrying out sintering after printing is containing the oxide semiconductor porous layer formation slurry of oxide semiconductor particle.
Oxide semiconductor porous layer formation slurry, except above-mentioned oxide semiconductor particle, also contains resin and the terpineol equal solvents such as polyethylene glycol.
As the printing process of oxide semiconductor layer formation slurry, such as, can use silk screen print method, scrape the skill in using a kitchen knife in cookery or stick coating method etc.
Sintering temperature looks the material of oxide semiconductor particle and different, but is generally 350 DEG C ~ 600 DEG C, and sintering time also looks the material of oxide semiconductor particle and different, but is generally 1 ~ 5 hour.
By obtaining work electrode 10 like this.
Then, above-mentioned photosensitive dye is adsorbed on the surface of oxide semiconductor layer 13 of work electrode 10.For this reason, work electrode 10 is impregnated in the solution containing photosensitive dye, this photosensitive dye is made to be adsorbed onto on oxide semiconductor layer 13, afterwards, unnecessary photosensitive dye is washed away with the solvent composition of above-mentioned solution, carry out drying, photosensitive dye is adsorbed onto on oxide semiconductor layer 13.But also can carry out drying after in the solution coat containing photosensitive dye to oxide semiconductor layer 13, thus photosensitive dye is adsorbed onto on oxide semiconductor layer 13.
Then, above-mentioned coadsorbent is adsorbed on the surface of oxide semiconductor layer 13 of work electrode 10., work electrode 10 is impregnated in the solution containing coadsorbent for this reason, makes this coadsorbent be adsorbed onto on oxide semiconductor layer 13, afterwards, wash away unnecessary coadsorbent with the solvent composition of above-mentioned solution, carry out drying, coadsorbent is adsorbed onto on oxide semiconductor layer 13.But also can carry out drying after in the solution coat containing coadsorbent to oxide semiconductor layer 13, thus coadsorbent is adsorbed onto on oxide semiconductor layer 13.
Now, on the surface of oxide semiconductor layer 13, coadsorbent is adsorbed on and is not adsorbed with on the region of photosensitive dye.
In addition, coadsorbent also can mix with photosensitive dye and be adsorbed on the surface of oxide semiconductor layer 13 simultaneously.In this case, as long as oxide semiconductor layer 13 is immersed in the solution containing photosensitive dye and coadsorbent.Now, oxide semiconductor layer 13 dip time is in the solution preferably 10 ~ 48 hours, is more preferably 15 ~ 25 hours.
Then, oxide semiconductor layer 13 configures electrolyte 40.Electrolyte 40 such as configures by print processes such as silk screen printings.
Then, as shown in figure 41, the sealing organizator forming sealing 30 is got out.Sealing organizator, by getting out sealing resin film, sealing resin molding is formed the opening of a quadrangle and obtains.
Then, sealing portion organizator is bonded on work electrode 10.Sealing portion organizator to the bonding of work electrode 10 by sealing organizator heating and melting is carried out.
Then, be ready to electrode 20, be fitted on sealing organizator in the mode of the opening blocking sealing organizator, work electrode 10 and to electrode 20 between form sealing 30.Can under atmospheric pressure carry out also can under reduced pressure carrying out to the laminating on sealing organizator to electrode 20, but preferably under reduced pressure carry out, in addition, now, also can in advance to also adhesive seal portion organizator on electrode 20, by make bonding between sealing organizator and work electrode 10 and to electrode 20 between form sealing 30.
Low-light (level) DSSC 100 is obtained by above method.
The present invention is not limited to above-mentioned execution mode.Such as, in the above-described embodiment, the nesa coating 12 of transparent conductive substrate 15 is provided with oxide semiconductor layer 13, but oxide semiconductor layer 13 also can be arranged on on electrode 20.
In addition, in the above-described embodiment, electrode 20 is made up of conductive board 21 and catalyst layer 22, but also can be the same with work electrode 10 to electrode 20, be made up of transparency carrier 11 and nesa coating 12 disposed thereon.
Embodiment
Below, by enumerating embodiment, more specific description is carried out to content of the present invention, but the present invention is not limited to following embodiment.
Embodiment 1
First, the transparent conductive substrate that nesa coating that the FTO being 1 μm forms is formed is got out be formed by thickness on the transparency carrier that the thickness be made up of glass is 1mm.Then, carry out pattern formation with CO2 laser (UniversalSystem Products V-460), form 4 nesa coatings lining up 1 row.Formed by pattern, make 4 nesa coatings have the rectangular-shaped body of 3cm × 5cm respectively, and make to be spaced apart 0.5mm between body.In addition, for 3 nesa coatings in 4 nesa coatings, two extensions stretched out are formed respectively from the dual-side portion of body, and the extension of the position of the relative side of the side portion forming the body extending to the nesa coating corresponding with adjacent DSC respectively from two extensions.Now, make that the length of stretching out direction of extension is 1cm, the width of extension is 3mm.In addition, make that the width of extension is 2mm, the length of the bearing of trend of extension is 2cm.
Then, the oxide semiconductor layer formation slurry of coating containing titanium dioxide on the body of nesa coating, after drying, sinters 1 hour at 500 DEG C.Like this, the work electrode with oxide semiconductor layer is just obtained.
Then, the slurry containing low-melting glass is applied to region between body by silk screen printing, afterwards, in the region between adjacent body, forms the insulating material be made up of low-melting glass.
Then, by work electrode containing the photosensitive dye 0.3mmol that is made up of N719 and the coadsorbent 3mmol be made up of deoxycholic aicd (DCA), flood diel with in the dye solution that is solvent by acetonitrile and the tert-butyl alcohol by the mixed solvent that the volume ratio of 1 ︰ 1 mixes, afterwards, take out, dry, thus photosensitive dye on supporting on oxide semiconductor layer, and the upper coadsorbent of absorption.
Then, the electrolyte of coating containing iodine oxidation-reduction pair on oxide semiconductor layer, configuration electrolyte.Now, the I in electrolyte is made
3 -concentration is 3 × 10
-6mol/L.
Then, the 1st sealing organizator of formation the 1st sealing is ready for.1st sealing organizator is by getting out 1 ethylene-methacrylic acid copolymer (trade name: Nucrel by 12cm × 5cm × 50 μm, Mitsui DuPont Chemicals product) the sealing resin film that forms, sealing resin molding is formed the opening of 4 quadrangles and obtains.Now, each opening of the 1st sealing organizator is made to be the size of 2.8cm × 4.8cm × 50 μm and width is 1mm.
1st sealing organizator is placed on the working electrode (s, bonded on the working electrode (s by heating and melting.
Then, 4 are got out to electrode.The each pair of electrode is that the catalyst layer be made up of platinum of 10nm is ready to by forming thickness with sputtering method on the titanium foil of 2.95cm × 5cm × 40 μm.In addition, then prepare an above-mentioned 1st sealing organizator, by method same as described above 1st sealing organizator is bonded in in electrode with in work electrode one side in opposite directions.
Then, make bonding the 1st sealing organizator on the working electrode (s and be bonded in the 1st sealing organizator on electrode in opposite directions, making to overlap between the 1st sealing formed body.Then, limit adds flanging to the 1st sealing organizator and makes its heating and melting in this condition.Like this, work electrode and to electrode between define the 1st sealing.
Then, the 2nd sealing is got out.The sealing resin film that 2nd sealing is made up of the maleic anhydride modified polyethylene (trade name: Bynel, E.I.Du Pont Company's product) of 13cm × 6cm × 50 μm preparation 1, sealing resin molding is formed the opening of 4 quadrangles and obtains.Now, make each opening of the 2nd sealing be the size of 2.8cm × 4.8cm × 50 μm and peripheral part width be 1.5mm, the width of the separating part of separating side opening in peripheral part is the mode of 1mm.2nd sealing is fitted on electrode the mode of electrode edge to clamp together with the 1st sealing.Now, while by the 2nd sealing by being pressed in the 2nd sealing top by the 1st sealing and the 2nd sealing heating and melting, thus the 2nd sealing is fitted on electrode and the 1st sealing.
Finally, prepare the silver paste (Teng Cang changes into Products, D-500) of low temperature curing type, be coated with to the extension of electrode to the nesa coating corresponding with adjacent DSC, solidify 12 hours at 30 DEG C.Like this, the electric conducting material of the extension connected electrode and the nesa coating corresponding with adjacent DSC is formed with silver.The size of electric conducting material is 7mm × 10mm × 10 μm.Obtain DSC module like this.
Embodiment 2 ~ 22 and comparative example 1 ~ 6
Except by photosensitive dye, coadsorbent 1, coadsorbent 2 and I
3 -concentration (unit for μM) change as shown in Table 1 and Table 2 beyond, obtain DSC module by the method identical with embodiment 1.
Embodiment 23 and 24
Except by photosensitive dye, coadsorbent 1, coadsorbent 2 and I
3 -concentration (unit for μM) as shown in table 2 change beyond, obtain DSC module by the method identical with embodiment 1.Now, coadsorbent 2 is made to be 3 relative to the mol ratio of coadsorbent 1.
As shown in Table 1 and Table 2, open voltage Voc when 100 lux determining to the DSC module by embodiment 1 ~ 24 and comparative example 1 ~ 6 gained and photoelectric conversion efficiency.Here, for photoelectric conversion efficiency η, measure respectively when illumination is respectively 10 luxs, 100 luxs, 1000 luxs, 10000 luxs, 20000 lux.Result is shown in table 1 and table 2.
As shown in Table 1 and Table 2, for the DSC module by embodiment 1 ~ 24 gained, under the illumination of 100 luxs (mensuration light source is fluorescent lamp), there is open voltage ratio by the large tendency of the DSC module of comparative example 1 ~ 6 gained.
In addition, for the DSC module by embodiment 1 ~ 24 gained, below 10000 luxs (mensuration light source is fluorescent lamp) illumination under photoelectric conversion efficiency be all greater than photoelectric conversion efficiency not under the illumination (20000 lux) of above-mentioned illumination range.And it is sometimes substantially identical with the photoelectric conversion efficiency not under the illumination of above-mentioned scope by the photoelectric conversion efficiency under illumination below 1000 luxs of the DSC module of comparative example 1 ~ 6 gained.
By being confirmed above, according to low-light (level) DSC of the present invention, there is under low-light (level) environment excellent light transfer characteristic.
Table 1
Table 2
A ~ Q in table 1 and table 2 represents following compound.In addition, the oxygen atom (O) of the OH base in the organic compound that numeric representation formula (2) ~ (4) in the bracket of A ~ H, P and Q or formula (X) represent and apart from the length between this oxygen atom (O) atom farthest.
A: deoxycholic aicd (DCA, 1.5nm)
B: chenodeoxycholic acid (1.5nm)
C: cholic acid (1.5nm)
D:4-guanidine radicals butyric acid (1nm)
E:3-benzenpropanoic acid (0.9nm)
F:2,3-pyridinedicarboxylic acid (0.9nm)
G：
[changing 28]
（1.7nm）
H：
[changing 29]
（1.7nm）
I: dodecoic acid
J: malic acid
K：
[changing 30]
Two (3,3-dimethylbutyl) phosphinic acids (DINHOP)
L：
[changing 31]
2-cetyl malonic acid (HDMA)
M：
[changing 32]
Positive decylphosphonic acid (DPA)
N：
[changing 33]
Decyl trimethoxy silane
O：
[changing 34]
Trifluoro propyl trimethoxy silane
The P:5-tert-butyl group-2-pyridine carboxylic acid (0.8nm)
Q: the tert-butyl alcohol (0.4nm)
Symbol description:
10 ... work electrode
11 ... transparency carrier
12 ... nesa coating
13 ... oxide semiconductor layer
15 ... transparent conductive substrate (the 1st electrode)
20 ... to electrode (the 2nd electrode)
100 ... DSSC
Claims (9)
1. low-light (level) DSSC, it comprises
There is transparency carrier and be arranged on the nesa coating on described transparency carrier the 1st electrode,
With described 1st electrode the 2nd electrode in opposite directions,
Be arranged on the oxide semiconductor layer on described 1st electrode or described 2nd electrode,
Be arranged on the electrolyte between described 1st electrode and described 2nd electrode,
Be adsorbed on photosensitive dye on described oxide semiconductor layer and
The coadsorbent on described oxide semiconductor layer is adsorbed on together with described photosensitive dye,
Described photosensitive dye is the metal complex that following formula (1) represents,
Described coadsorbent contains the 2 kinds of organic compounds be selected from organic compound that described formula (2) ~ (4) represent, or containing the organic compound that the organic compound be selected from organic compound that described formula (2) ~ (4) represent and following formula (X) represent
Described coadsorbent comprises following 1st organic compound and the 2nd organic compound:
In the organic compound that described formula (2) ~ (4) represent, 1st organic compound be in the organic compound that represents of described formula (2) ~ (4) from the oxygen atom of OH base to being the organic compound of 0.7 ~ 3nm from the 1st length this oxygen atom atom farthest
In the organic compound that described formula (2) ~ (4) and formula (X) represent, 2nd organic compound be in the organic compound that represents of described formula (2) ~ (4) or formula (X) from the oxygen atom of OH base to being the organic compound of 0.1 ~ 0.7nm from the 2nd length this oxygen atom atom farthest
Described 1st length of described 1st organic compound is larger than described 2nd length of described 2nd organic compound,
In formula (1), M represents Ru, R
1, R
2, R
3and R
4separately represent monovalent cation, R
5and R
6separately represent halogen ,-H ,-CN ,-NCS or-NCO;
In formula (2), n represents the integer of 0 ~ 5, R
7represent and there is the univalent perssad of pi-conjugated structure or there is the univalent perssad of steroid backbone;
In formula (3), W represents carbon atom or silicon atom, Y
1, Y
2, Y
3and Y
4separately represent that hydrogen atom, carboxyl, carbon number are the replacement of 1 ~ 6 or are the replacement of 3 ~ 20 or the alkyl without replacement without the alkoxyl replaced or carbon number, Y
1, Y
2, Y
3and Y
4in one represent carbon number be 3 ~ 20 replacement or without the alkyl replaced, in all the other at least two represent carboxyls or carbon number be 1 ~ 6 replacement or without the alkoxyl replaced;
In formula (4), Y
5, Y
6and Y
7separately represent that hydroxyl or carbon number are the replacement of 3 ~ 20 or the alkyl without replacement, Y
5, Y
6and Y
7in one or two represent carbon numbers be 3 ~ 20 replacement or without replace alkyl, all the other represent hydroxyl;
In formula (X), A
1~ A
3separately represent hydrogen atom or methyl, A
4represent hydroxyl or carboxyl.
2. DSSC according to claim 1, is characterized in that, the R in described formula (2)
7in, described in there is pi-conjugated structure univalent perssad be the univalent perssad with merocyanine skeleton, phenyl skeleton, guanidine skeleton, pyridine skeleton or porphyrin skeleton,
The described univalent perssad with steroid backbone is the univalent perssad that following formula (5) represents,
There is the univalent perssad of steroid backbone
In formula (5), R
34, R
35and R
36separately represent hydrogen atom or hydroxyl.
3. DSSC according to claim 2, is characterized in that, the R in described formula (2)
7in, described in there is pi-conjugated structure univalent perssad be the univalent perssad that there is merocyanine skeleton or there is guanidine skeleton.
4. the DSSC according to any one of claims 1 to 3, is characterized in that, in described formula (1), and R
1, R
2, R
3and R
4in at least one be hydrogen ion.
5. the DSSC according to any one of claims 1 to 3, is characterized in that, in described formula (1), and R
1, R
2, R
3and R
4in at least one be hydrogen ion, all the other are monovalence ammonium salt.
6. DSSC according to claim 4, is characterized in that, in described formula (1), and R
5and R
6for-NCS.
7. DSSC according to claim 5, is characterized in that, R
5and R
6for-NCS.
8. the DSSC according to any one of claims 1 to 3, is characterized in that, described coadsorbent is 0.1 ~ 1 relative to the mol ratio of described photosensitive dye.
9. the DSSC according to any one of claims 1 to 3, is characterized in that, described electrolyte contains by I
-and I
3 -the oxidation-reduction pair formed, the I in described electrolyte
3 -concentration at below 0.006mol/L.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-044732 | 2011-03-02 | ||
| JP2011044732 | 2011-03-02 | ||
| PCT/JP2012/054845 WO2012118044A1 (en) | 2011-03-02 | 2012-02-27 | Dye-sensitized solar cell for low light intensities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103380535A CN103380535A (en) | 2013-10-30 |
| CN103380535B true CN103380535B (en) | 2015-10-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280009011.5A Expired - Fee Related CN103380535B (en) | 2011-03-02 | 2012-02-27 | Low-light (level) DSSC |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20140000715A1 (en) |
| EP (1) | EP2683019B1 (en) |
| JP (1) | JP5634594B2 (en) |
| CN (1) | CN103380535B (en) |
| WO (1) | WO2012118044A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0723103T3 (en) * | 1995-01-19 | 2000-12-18 | Legris Sa | Device for quick coupling of a pipe to a rigid element |
| JP6059262B2 (en) * | 2015-01-26 | 2017-01-11 | 田中貴金属工業株式会社 | Dye-sensitized solar cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1473745A1 (en) * | 2003-04-30 | 2004-11-03 | Ecole Polytechnique Federale De Lausanne (Epfl) | Dye sensitized solar cell |
| JP2005251736A (en) * | 2004-02-02 | 2005-09-15 | Hitachi Maxell Ltd | Photoelectric conversion element, photocell using it and case of electronic equipment |
| JP2006278112A (en) * | 2005-03-29 | 2006-10-12 | Sharp Corp | Dye-sensitized solar cell and dye-sensitized solar cell module |
| JP2010040432A (en) * | 2008-08-07 | 2010-02-18 | Shimane Prefecture | Dye-sensitized solar cell and partition forming method |
| EP2230702A1 (en) * | 2009-03-19 | 2010-09-22 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Modified surface |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004127579A (en) * | 2002-09-30 | 2004-04-22 | Fuji Photo Film Co Ltd | Manufacturing method of metal-metal oxide composite electrode, photoelectric transducing element and photoelectric cell |
| JP5096673B2 (en) * | 2004-11-30 | 2012-12-12 | 三菱製紙株式会社 | Semiconductor electrode and photoelectric conversion element |
| JP4931402B2 (en) * | 2005-11-14 | 2012-05-16 | Ｊｘ日鉱日石エネルギー株式会社 | Photoelectric conversion element |
| JP2007234580A (en) * | 2006-02-02 | 2007-09-13 | Sony Corp | Dye sensitized photoelectric conversion device |
| EP2296215A4 (en) * | 2008-06-24 | 2011-07-20 | Panasonic Elec Works Co Ltd | Dye-sensitized solar cell |
| JP2012004010A (en) * | 2010-06-18 | 2012-01-05 | Sony Corp | Photoelectric conversion element and its manufacturing method and electronic apparatus |
-
2012
- 2012-02-27 CN CN201280009011.5A patent/CN103380535B/en not_active Expired - Fee Related
- 2012-02-27 WO PCT/JP2012/054845 patent/WO2012118044A1/en active Application Filing
- 2012-02-27 EP EP12751907.2A patent/EP2683019B1/en not_active Not-in-force
- 2012-02-27 JP JP2013502351A patent/JP5634594B2/en active Active
-
2013
- 2013-09-03 US US14/016,448 patent/US20140000715A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1473745A1 (en) * | 2003-04-30 | 2004-11-03 | Ecole Polytechnique Federale De Lausanne (Epfl) | Dye sensitized solar cell |
| JP2005251736A (en) * | 2004-02-02 | 2005-09-15 | Hitachi Maxell Ltd | Photoelectric conversion element, photocell using it and case of electronic equipment |
| JP2006278112A (en) * | 2005-03-29 | 2006-10-12 | Sharp Corp | Dye-sensitized solar cell and dye-sensitized solar cell module |
| JP2010040432A (en) * | 2008-08-07 | 2010-02-18 | Shimane Prefecture | Dye-sensitized solar cell and partition forming method |
| EP2230702A1 (en) * | 2009-03-19 | 2010-09-22 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Modified surface |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103380535A (en) | 2013-10-30 |
| EP2683019A4 (en) | 2014-09-03 |
| JPWO2012118044A1 (en) | 2014-07-07 |
| EP2683019B1 (en) | 2015-08-19 |
| JP5634594B2 (en) | 2014-12-03 |
| WO2012118044A1 (en) | 2012-09-07 |
| EP2683019A1 (en) | 2014-01-08 |
| US20140000715A1 (en) | 2014-01-02 |
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